Polymerizable vinyl benzoates

ABSTRACT

Disclosed herein are monomeric compounds and methods of preparing these compounds which have the formula: ##STR1## wherein: R and R&#39; are independently selected from the group consisting of H, halide and alkyl; 
     Ar and Ar&#39; are independently arylene; 
     X is selected from the group consisting of NHSO 2  R 2 , CH 2  NHSO 2  R 2  and SO 2  NHR 2  and 
     R 2  is selected from the group consisting of alkyl, aryl and aralkyl. 
     These monomers are homopolymerized or copolymerized with one or more other monomers to yield polymers having desirable solubility characteristics. A particular use for the polymers is in relief image materials or as binders in photographic layers.

This application is a divisional of Ser. No. 329,548 now U.S. Pat. No.4,420,630.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to organic materials which are useful inpreparing polymers particularly useful in the graphic arts andphotographic arts. In one of its aspects, it relates to the use of suchmaterials to prepare polymers which are incorporated intoradiation-sensitive elements to obtain a desirable combination ofproperties.

2. Description of Related Art

The formation of polymerizable vinyl arylsulfonamide esters which aresoluble in acetone, which is the preferred solvent for coating polymericbinders for radiation-sensitive elements is described in U.S. Pat. No.4,259,469 issued Mar. 31, 1981 to the present inventors. These monomerswere formed by a simple condensation reaction of a vinyl aryl halidewith a hydroxy compound. The method of preparation of these monomers,however, results in only a limited range of monomers useful for thepurposes intended.

It would be highly desirable to have additional monomers which aresoluble in acetone and polymers thereof which are useful as binders forphotographic materials.

SUMMARY OF THE INVENTION

The present invention provides polymerizable vinylbenzoates which aresoluble in acetone, methyl ethyl ketone, tetrahydrofuran and dioxane,and are prepared by a novel method of preparation. The present inventionalso provides polymers formed from such monomers.

The polymers of the present invention are useful in many applications,but are particularly useful as copolymers in radiation-sensitivematerials used in the graphic arts. Such copolymers which can alsocomprise units of polymerized vinyl ethers having pendant aldehydegroups are crosslinked with reagents, such as amines, to provide organicsolvent insoluble areas. These insoluble areas in light-exposed regionsof a lithographic plate or photoresist provide negative relief images.Preferred uses for the polymers of this invention are disclosed in U.S.Pat. No. 4,247,625 issued Jan. 27, 1981.

Certain other copolymers comprise units of polymerized ethylenicallyunsaturated monomers having ionic groups which form copolymers solublein solvent systems, such as acetone-water mixtures, water, alcohol-watermixtures, methanol and the like. Such anionic or cationic copolymers aresuitable for aqueous processing.

The polymers of the present invention are also useful as binder vehiclesin a variety of applications, such as in various light-sensitivecompositions, subbing layers and the like.

One aspect of the present invention comprises a compound having theformula: ##STR2## wherein R and R' are independently selected from thegroup containing of hydrogen, halide or alkyl;

Ar and Ar' are independently arylene;

X is selected from the group consisting of NHSO₂ R², CH₂ NHSO₂ R² andSO₂ NHR² and

R² is selected from the group consisting of alkyl, aryl and aralkyl.

In another aspect of the present invention, a process of preparing thecompounds of formula (I) comprises

(1) reacting a phenol having the formula

    HO--Ar'--X                                                 (II)

with a benzoyl chloride having the formula

    BrCH.sub.2 CH.sub.2 --Ar--COCl                             (III)

wherein

Ar, Ar' and X are as defined above, and

(2) dehydrobrominating the product of step (1).

Still another aspect of the present invention comprises a polymer formedfrom: (a) about 1 to about 100 mole percent of one or more monomershaving formula (I) and (b) from 0 to about 99 mole percent of one ormore additional ethylenically unsaturated polymerizable monomers.

In still another aspect of the present invention a process of preparingthe above-described polymers comprises

(1) reacting a phenol having formula (II) with a benzoyl chloride havingformula (III),

(2) dehydrobrominating the product of step (1) and

(3) polymerizing the monomer formed in step (2) with 0 to 99 molepercent of one or more additional ethylenically unsaturatedpolymerizable monomers.

DETAILED DESCRIPTION OF THE INVENTION

The monomers of the present invention are depicted by the formula:##STR3## wherein: R and R' are independently hydrogen; halide, such asfluoride, chloride, bromide and iodide; or alkyl, preferably having from1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl andt-butyl, including substituted alkyl such as haloalkyl such aschloromethyl and 1,2-dibromoethyl.

Ar and Ar' are arylene, preferably having from 6 to 18 carbon atoms,including phenylene, naphthylene, phenylenedimethylene and diphenylene,which arylene is unsubstituted or substituted, for example, with alkyl,preferably containing 1 to 4 carbon atoms, halide, sulfonamido, nitro oralkoxy.

X is selected from the group consisting of NHSO₂ R², CH₂ NHSO₂ R² andSO₂ NHR² and

R² is selected from the group consisting of alkyl such as describedabove for R and R'; aryl such as phenyl and naphthyl includingsubstituted aryl such as chlorophenyl and methylphenyl; and aralkyl suchas benzyl.

Exemplary monomers corresponding to formula (I) include4-(methanesulfonamido)phenyl 4-vinylbenzoate,4-(α-methanesulfonamido)tolyl 4-vinylbenzoate,4-(N-methylsulfamoyl)phenyl 4-vinylbenzoate, N-methyl-4-sulfamoylphenyl4-vinylbenzoate, 4-(N-phenylsulfamoyl)phenyl 4-vinylbenzoate,4-(butanesulfonamido)phenyl 4-vinylbenzoate,4-(propanesulfonamido)phenyl 4-vinylbenzoate, 4-(benzenesulfonamido)phenyl 4-vinylbenzoate, 4-(ethanesulfonamido)phenyl4-vinylbenzoate and 4-(N-butylsulfamoyl)phenyl 4-vinylbenzoate.

Preferred monomers of the present invention are those having formula (I)wherein R and R' are hydrogen; Ar and Ar' are phenylene; and X is SO₂NHR² wherein R² is CH₃.

The novel process of preparing monomers of formula (I) comprises thefirst step of reacting a phenol having the formula HO--Ar'--X with abenzoyl chloride having the formula BrCH₂ CH₂ --Ar--COCl preferably inan organic solvent medium. Ar, Ar' and X are as defined above.

Useful phenols include N-(4-hydroxyphenyl)methanesulfonamide,N-(4-hydroxybenzyl)methanesulfonamide,N-phenyl-4-hydroxybenzenesulfonamide,N-(4-hydroxyphenyl)butanesulfonamide andN-methyl-4-hydroxybenzenesulfonamide.

Examples of useful benzoyl chlorides include p-(2-bromoethyl)benzoylchloride and 4-(2-bromoethyl)naphthoyl chloride. The reactants areprepared by known techniques. p-(2-Bromoethyl)benzoyl chloride isprepared according to the procedure of Foreman and McElvin, J. AmericanChemical Society, 62, 1435 (1940). N-substituted4-hydroxybenzenesulfonamides are prepared by the method of Wagner etal., J. Med. Chem., 8, 377 (1965). N-(4-hydroxyphenyl)sulfonamides areprepared by the method of Beckwith et al., J. Org. Chem., 19, 1708(1954). N-(4-hydroxybenzyl)sulfonamides are prepared by catalyticreduction of N-(4-hydroxybenzlidine)sulfonamides which are prepared bycondensing 4-hydroxybenzaldehyde with sulfonamides according to theprocedure described in Markov and Kosyan, Ukrainski Khinicheski Zhurnal,33(3), 299 (1967).

The described reactants are reacted in the presence of an acid acceptorwhich is defined as a compound which will react with the released haloacid condensate to form a salt and aid in shifting equilibrium toproduct. Exemplary acid acceptors include hydroxides, such as alkalimetal hydroxides, alkaline earth metal hydroxides, quarternary alkylammonium hydroxides and the like; alkoxides, such as aluminum butoxide,sodium ethoxide and the like; carbonates such as sodium carbonate,potassium carbonate and the like; trialkylamines such as triethylamine,tributylamine and the like; pyridine, picoline, weak base ion-exchangeresins, such as amberlite IR-4B and IR-45 and the like and others wellknown in the art. The acid acceptors are generally present in thereaction mixture in ratios of 1:1 to 2.2:1.0 with the hydroxy compound.

Although the ratio of reactants is variable, it is preferred that thereaction contain from about 1 to about 2 moles of phenol for every moleof benzoyl chloride.

If desired, a mutual inert solvent is employed to dissolve thereactants. The products are removed from the reaction solvent by anysuitable means such as filtration, concentration and the like. Theamount of solvent used is not critical and preferably between about 75and 99 weight percent of the reaction mixture. Suitable solvents includechlorinated solvents, such as methylene chloride, ethylene chloride andthe like, diethyl ether, tetrahydrofuran and the like.

The reaction generally proceeds at a temperature between about -10° C.and 10° C. and preferably between about -5° C. to about 0° C. Thereaction pressure can be from subatmospheric to superatmosphericpressures of 1000 PSIG or higher. Generally the reaction is carried outat atmospheric pressure.

The reaction time is a function of reaction temperature, pressure andthe particular reactants employed. In general, reaction times arebetween 0.5 and 4 hours.

The reaction product is dehydrobrominated to form the useful monomer.The dehydrobromination process comprises treatment of the reactionproduct with an alkaline reagent, preferably potassium carbonate in thepresence of acetone, at room temperature for 48 hours to yield thevinylbenzoate monomer.

The monomers described herein are useful in making the acetone-solublepolymers of the present invention.

The polymers comprise about 1 to 100 mole percent of one or morepolymerized monomers of the described formula (I). Mixtures of suchmonomers can be used, if desired, in forming the polymers.

The copolymers can comprise up to 99 mole percent of recurring unitsderived from one or more additional ethylenically unsaturatedpolymerizable monomers, each containing, for example, at least one

    --CH═C< or CH.sub.2 ═C<

group. Exemplary monomers include, for example, vinyl esters, such asvinyl acetate, vinyl butyrate and the like; vinyl amides, such asacrylamide, methacrylamide, N-methylacrylamide, N-isopropylacrylamide;vinyl nitriles, such as acrylonitrile, methylacrylonitrile, 3-butenenitrile and the like; vinyl ketones, such as methyl vinyl ketone and thelike; vinyl halides, such as vinyl chloride, vinyl bromide, vinylidenechloride and the like; vinyl ethers, such as allyl phenyl ether, methylvinyl ether, and o-formylphenyl vinylbenzyl ether; α,β-unsaturated acidsor esters thereof, such as acrylic acid, methacrylic acid, methylacrylate, butyl methacrylate, 2-dimethylaminoethyl methacrylate,2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, m-formylphenylmethacrylate and the like; olefins and diolefins, such as ethylene,propylene, butadiene, isoprene, 1,1-diphenylethylene and the like; vinylaromatics, such as styrene, α-methylstyrene, p-chlorostyrene and thelike; 4,4,9-trimethyl-8-oxo-7-oxa-4-azonia-9-decene-1-sulfonate;2-(methacryloyloxy)ethyltrimethylammonium methosulfate;N-vinylsuccinimide; N-vinylphthalimide; N-vinylpyrazolidone and thelike. Mixtures of monomers can be used, if desired.

In one preferred embodiment of the present invention, noveluncrosslinked polymers which are soluble in acetone, tetrahydrofuran andmethyl ethyl ketone and the like, are formed from:

(a) about 1 to about 99 mole percent of one or more monomers havingformula (I); and

(b) about 1 to about 99 mole percent of one or more additionalethylenically unsaturated polymerizable monomers containing pendantaldehyde groups which crosslink with reagents, such as amines.

Exemplary of such aldehyde-containing monomers include m-formylphenylmethacrylate, m-formylphenyl acrylate, acrylamidoacetaldehyde,p-(2-methacryloyloxyethoxy)benzaldehyde and the like, as described inU.S. Pat. No. 2,929,710, which is incorporated herein by reference; andmonomers having the formula (IV), ##STR4## wherein: R⁴, R⁵, R⁶ and R⁷are independently hydrogen; or alkyl having from 1 to 4 carbon atoms,such as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl and thelike;

R⁸ is arylene having from 6 to 18 carbon atoms, such as phenylene,naphthylene, anthrylene, biphenylylene, including arylenes substitutedwith any of the above substituents;

m is an integer of from 1 to 4; and

n is an integer of from 0 to 4.

Exemplary monomers corresponding to formula (IV) include o-, p- orm-formylphenyl vinylbenzyl ether; o-, p- or m-(2-formylethoxy)phenylvinylbenzyl ether; 2-, 3- or 4-formylnaphthyl vinylbenzyl ether;formylbiphenylyl vinylbenzyl ether; o- or p-formyl-2-methylphenylvinylbenzyl ether; o-, p- or m-formylphenyl α-chlorovinylphenylethylether and the like. Mixtures of these monomers can be used, if desired.

Preferred polymers of the present invention formed from monomers havingformula (IV) are those wherein R⁴, R⁵, R⁶ and R⁷ are all hydrogen, andmost preferably when, additionally, m is 1 and n is 0. Particularlypreferred polymers are obtained when R⁸ is phenylene, including suchmonomers as o-, p- or m-formylphenyl vinylbenzyl ether.

Methods of preparing monomers of formula (IV) are discussed in U.S. Pat.No. 4,225,689, issued Sept. 30, 1980.

In another embodiment, novel copolymers soluble in acetone-water,methanol, methanol-water and water solvent systems when used in minoramounts are suitable for aqueous coating and processing. Thesecopolymers can be formed from:

(a) about 1 to about 99 mole percent of one or more monomers havingformula (I); and

(b) about 1 to about 99 weight percent of one or more additionalethylenically unsaturated polymerizable monomers having ionic groups.

Examples of such copolymerizable monomers include the following and/ortheir salts:

N-(2-methacryloyloxyethyl)-N,N,N-trimethylammonium methosulfate

N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride

Aconitic acid

2-Acrylamido-2-methylpropanesulfonic acid

3-Acrylamidopropane-1-sulfonic acid

Acrylic acid

Methacrylic acid

4-Acryloyloxybutane-1-sulfonic acid

3-Acryloyloxypropionic acid

3-Acryloyloxybutane-1-sulfonic acid

3-Acryloyloxypropane-1-sulfonic acid

4-t-Butyl-9-methyl-8-oxo-7-oxa-4-aza-9-decene-1-sulfonic acid

α-Chloroacrylic acid

Maleic acid

Chloromaleic acid

2-Methacryloyloxyethyl-1-sulfonic acid

Citraconic acid

Crotonic acid

Fumaric acid

Mesaconic acid

α-Methyleneglutaric acid

Monoethyl fumarate

Monomethyl α-methyleneglutarate

Monomethyl fumarate

Vinylsulfonic acid

p-Styrenesulfonic acid

4-Vinylbenzylsulfonic acid

Acryloyloxymethylsulfonic acid

4-Methacryloyloxybutane-1-sulfonic acid

2-Methacryloyloxyethane-1-sulfonic acid

3-Methacryloyloxypropane-1-sulfonic acid

2-Acrylamido-2-methylpropane-1-sulfonic acid

2-Methacrylamido-2-methylpropane-1-sulfonic acid

3-Acrylamido-3-methylbutane-1-sulfonic acid; and

Maleic anhydride.

The preferred monomer having an ionic group isN-(2-methacryloyloxy)ethyltrimethylammonium methosulfate.

Although the amount of polymerized monomer of formula (I) incorporatedin the polymers of the present invention can vary from about 1 to about100 mole percent, preferably the amount is from about 50 to about 99mole percent. The preferred amount of additional ethylenicallyunsaturated polymerizable monomers is from about 0 to about 50 molepercent.

Exemplary polymers of the present invention includepoly[4-(α-methanesulfonamido)tolyl 4-vinylbenzoate],poly[4-(methanesulfonamido)phenyl 4-vinylbenzoate],poly(N-phenyl-4-sulfamoylphenyl 4-vinylbenzoate andpoly(N-methyl-4-sulfamoylphenyl 4-vinylbenzoate).

The process of preparing the polymers of the present invention comprisesthree steps, the first two being that of making the monomer by themethod described earlier. The third step comprises homopolymerization ofthese monomers or copolymerization with each other, or with theadditional ethylenically unsaturated polymerizable monomers.

Polymerization can be carried out using techniques available to thoseskilled in the polymer chemistry art, including bulk, suspension,emulsion, solution and continuous techniques. Preferably, it is carriedout in organic solvent solutions, usually solvents such as p-dioxane,N,N-dimethylformamide, tetrahydrofuran and the like, and most preferablyin N,N-dimethylformamide.

The temperature at which the polymers of the present invention areprepared is subject to wide variation, since this temperature dependsupon such variable features as the specific monomers used, duration ofheating, pressure employed and like considerations. However, thepolymerization temperature generally does not exceed about 110° C., andmost often it is in the range of about 40° to about 100° C. Thepolymerization can be carried out in a suitable vehicle, for example,water or mixtures of water with water-miscible solvents, as exemplifiedby methanol, ethanol, propanol, isopropyl alcohol, butyl alcohol and thelike when emulsion or suspension techniques are used. The pressureemployed in the polymerization, if any, is usually only sufficient tomaintain the reaction mixture in liquid form, although eithersuperatmospheric or subatmospheric pressures can be used. Theconcentration of polymerizable monomer in the polymerization mixture canbe varied widely with concentrations up to about 80 percent by weight,and preferably from about 10 to about 50 percent by weight, based on theweight of the vehicle, being satisfactory. Suitable catalysts for thepolymerization reaction include, for example, from about 0.001 to about2.0 weight percent of free radical catalysts, such as hydrogen peroxide,cumene hydroperoxide, azotype initiators and the like. In redoxpolymerization systems, conventional ingredients can be employed. Ifdesired, the polymer can be isolated from the reaction vehicle byfreezing, salting out, precipitation in a non-solvent, such as diethylether, or any other procedure suitable for this purpose.

As indicated in U.S. Pat. No. 3,142,568, issued July 28, 1964, it issometimes advantageous to include a surface active agent or compatiblemixtures of such agents in emulsion or suspension preparation of vinylor addition polymers. Suitable wetting agents include the nonionic,ionic and amphoteric types, as exemplified by the polyoxyalkylenederivatives, amphoteric amino acid dispersing agent, includingsulfobetaines and the like. Such wetting agents are disclosed in U.S.Pat. Nos. 2,600,831, issued July 17, 1952; 2,271,622, issued Feb. 3,1942; 2,271,623, issued Feb. 3, 1942; 2,275,727, issued Mar. 10, 1942;2,787,604, issued Apr. 2, 1957; 2,816,920, issued Dec. 17, 1957 and2,739,891, issued Mar. 27, 1956.

The equivalent molecular weights of the polymers of the presentinvention are subject to wide variation, but typically can be within therange of from about 10,000 to about 500,000. These polymers generallyhave inherent viscosities within the range of from about 0.10 to 4.5,and preferably from about 0.4 to about 1.2, as measured (unlessotherwise indicated in this specification) in N,N-dimethylformamide(DMF) (0.25 g polymer in 100 ml solution) at 25° C. As used herein, theterm "inherent viscosity" is determined by the formula: ##EQU1##wherein: η_(inh) is the inherent viscosity;

η_(rel) is the relative viscosity of a DMF solution of the polymer; and

C is the concentration in grams (0.25) of polymer per 100 cc ofsolution.

The polymers of the present invention typically have glass transitiontemperatures within the range of about -10° C. to about 200° C. Thesetemperatures can be determined by differential scanning colorimetry, asdisclosed in Techniques and Methods of Polymer Evaluation, Volume 2,Marcel Dekker, Inc., New York, 1970.

The polymers of the present invention are soluble in a variety oforganic solvents, including acetone, tetrahydrofuran,N,N-dimethylformamide, methyl ethyl ketone and the like. Typically,these solvents are used in the graphic arts to remove unexposed areas ofphotoresists or lithographic plates. Developer solvents have asolubility such that the crosslinking of the polymer results in adistinct solubility differential in organic solvents such that saidsolvents will dissolve uncrosslinked polymer but not crosslinkedpolymer, and for imaging compositions such as described in U.S. Pat. No.4,239,848, issued Dec. 16, 1980, solubility is about 1.9 g of polymerdissolved in 9.6 cc of acetone. The crosslinkable polymers becomeinsoluble after they are crosslinked.

The polymers of the present invention are particularly useful as bindersin an imaging system comprising an aromatic dialdehyde capable ofreacting with amines to form a dye, a material capable of generatingamines in response to activating radiation and a binder that providesimproved maximum densities for such an imaging system, such as describedin U.S. Pat. No. 4,239,848, issued Dec. 16, 1980.

The polymers are compatible with radiation-sensitive compositions andare thus useful as binders for these materials in coating compositions.

This invention is further illustrated by the following examples,although it will be understood that these examples are included merelyfor purposes of illustration, and are not intended to limit the scope ofthe invention.

EXAMPLES 1-4 (a) Synthesis of 4-(Methanesulfonamido)phenyl4-(2-bromoethyl)benzoate

To a mixture of 6.05 g (0.0323 mol) of N-(4-hydroxylphenyl)methanesulfonamide, 3.27 g (0.0323 mol) of triethylamine and 100 ml ofmethylene chloride was added a solution of 8.0 g (0.0323 mol) ofp-(2-bromoethyl)benzoyl chloride in 75 mL of methylene chloridedropwise.

The reaction mixture was stirred for 4 hours at room temperature. Theresultant solution was washed with 2% hydrochloric acid and twice withwater, dried over magnesium sulfate and concentrated on a rotaryevaporator to a white solid. Recrystallization from 700 ml of 1:1ethanol:water gave 10.75 g (83.5% of theory) of4-(methanesulfonamido)phenyl 4-(2-bromoethyl)benzoate; mp=161°-2° C.

Analysis calculated for C₁₆ H₁₆ BrNO₄ S: C, 48.3; H, 4.0; Br, 20.1; N,3.5; S, 8.1. Found: C, 48.4; H, 4.3; Br, 20.6; N, 3.7; S, 7.6.

Properties of the ethyl, propyl, and phenyl analogues similarly preparedare found in Table I.

(b) Synthesis of 4-(Methanesulfonamido)phenyl 4-vinylbenzoate

A mixture of 10.0 g (0.02511 mol) of 4-(methanesulfonamido)phenyl4-(2-bromoethyl)benzoate, 3.47 g (0.02511 mol) of potassium carbonateand 100 ml of acetone was stirred at room temperature for 48 hours. Theresultant mixture was filtered and the filtrate was condensed to asolid. Recrystallization from 1:1 1,2-dichloroethane:hexane gave 4.2 g(52.7% of theory) of 4-(methanesulfonamido)phenyl 4-vinylbenzoate;mp=172°-3° C.

Analysis calculated for C₁₆ H₁₅ NO₄ S: C, 60.5; H, 4.8; N, 4.4; S, 10.1.Found: C, 59.7; H, 5.1; N, 4.5; S, 10.7.

Properties of the ethyl, propyl and phenyl analogues similarly preparedare found in Table II.

EXAMPLE 5 (a) Synthesis of 4-(α-Methanesulfonamido)tolyl4-(2-bromoethyl)benzoate

To a mixture of 20.13 g (0.10 mol) ofN-(4-hydroxybenzyl)methanesulfonamide, 10.2 g (0.10 mol) oftriethylamine and 300 ml of methylene chloride cooled to 0° C., wasadded a solution of 24.75 g (0.10 mol) of p-(2-bromoethyl)benzoylchloride in 100 ml of methylene chloride over approximately 40 minutes.The mixture was stirred for another 45 minutes, filtered, washed threetimes with water and dried over magnesium sulfate. After concentratingon a rotary evaporator, the residue was recrystallized from 1900 ml of1:1 1,2-dichloroethane:hexane to yield 23.5 g (57.0% of theory) of4-(α-methanesulfonamido)tolyl 4-(2-bromoethyl)benzoate; mp=141°-3° C.

Analysis calculated for C₁₇ H₁₈ BrNO₄ S: C, 49.5; H, 4.4; Br, 19.4; N,3.4; S, 7.8. Found: C, 49.0; H, 4.4; Br, 19.3; N, 3.4; S, 8.2.

(b) Synthesis of 4-(α-Methanesulfonamido)tolyl 4-vinylbenzoate

A mixture of 20.62 g (0.05 mol) of 4-(α-methanesulfonamido)tolyl4-(2-bromoethyl)benzoate, 6.91 g (0.05 mol) of potassium carbonate and200 ml of acetone was stirred at room temperature for approximately 55hours. The mixture was filtered and the filtrate was concentrated to awhite solid. All solids were combined, washed with water andrecrystallized from acetonitrile. The yield of4-(α-methanesulfonamido)tolyl 4-vinylbenzoate was 9.3 g (56.2% oftheory); mp=167°-8° C.

Analysis calculated for C₁₇ H₁₇ NO₄ S: C, 61.6; H, 5.2; N, 4.2; S, 9.7.Found: C, 61.3; H, 5.1; N, 4.4; S, 9.5.

EXAMPLES 6-7 (a) Synthesis of 4-(N-phenylsulfamoyl)phenyl4-(2-bromoethyl)benzoate

To a mixture of 24.93 g (0.10 mol) ofN-phenyl-4-hydroxybenzenesulfonamide, 10.12 g (0.10 mol) oftriethylamine and 150 ml of methylene chloride was added, dropwise, asolution of 24.75 g (0.10 mol) of 4-(2-bromoethyl)benzoyl chloride in150 ml of methylene chloride over a period of 12 minutes. The reactionmixture was stirred at room temperature for 3 hours, after which 500 mlof methylene chloride were added. The solution was washed once with 2%HCl and twice with water, dried over magnesium sulfate and concentratedto a white solid. Recrystallization from ethanol gave 39.7 g (86.1% oftheory) of 4-(N-phenylsulfamoyl)phenyl 4-(2-bromoethyl)benzoate,mp=156°-7° C.

Analysis calculated for C₂₁ H₁₈ BrNO₄ S: C, 54.8; H, 3.9; Br, 17.4; N,3.0; S, 7.0. Found: C, 54.7; H, 4.1; Br, 17.4; N, 3.4; S, 7.4.

Properties of the N-butyl analogue, similarly prepared, are found inTable I.

(b) Synthesis of 4-(N-phenylsulfamoyl)phenyl 4-vinylbenzoate

A mixture of 18.5 g (0.0402 mol) of 4-(N-phenylsulfamoyl)phenyl4-(2-bromoethyl)benzoate, 5.55 g (0.0402 mol) of potassium carbonate and250 ml of acetone was stirred at room temperature for approximately 48hours. The mixture was filtered and concentrated to an oily solid.Recrystallization from ethanol:water gave 11.7 g (76.7% of theory) of4-(N-phenylsulfamoyl)phenyl 4-vinylbenzoate; mp=59°-60° C.

Analysis calculated for C₂₁ H₁₇ NO₄ S: C, 66.5; H, 4.5; N, 3.7; S, 8.5.Found: C, 65.8; H, 4.3; N, 3.7; S, 9.0.

Properties of the similarly prepared N-butyl analogue are found in TableII.

The following Tables I and II illustrate the properties of Examples 1-7.

                                      TABLE I                                     __________________________________________________________________________     ##STR5##                                                                                              Anal.                                                                         Calculated  Found                                    Example                                                                            X         Yield, %                                                                           M.P., °C.                                                                   C  H N S Br C  H N S Br                              __________________________________________________________________________    (5a)                                                                                ##STR6## 57.0 141-3                                                                              49.5                                                                             4.4                                                                             3.4                                                                             7.8                                                                             19.4                                                                             49.0                                                                             4.4                                                                             3.4                                                                             8.2                                                                             19.3                            (4a)                                                                                ##STR7## 79.5 150-2                                                                              54.8                                                                             3.9                                                                             3.0                                                                             7.0                                                                             17.4                                                                             54.6                                                                             4.0                                                                             3.2                                                                             7.8                                                                             18.0                            (1a) NHSO.sub.2 CH.sub.3                                                                     83.5 161-2                                                                              48.3                                                                             4.0                                                                             3.5                                                                             8.1                                                                             20.1                                                                             48.4                                                                             4.3                                                                             3.7                                                                             7.6                                                                             20.6                            (6a)                                                                                ##STR8## 86.1 156-7                                                                              54.8                                                                             3.9                                                                             3.0                                                                             7.0                                                                             17.4                                                                             54.7                                                                             4.1                                                                             3.4                                                                             7.4                                                                             17.4                            (7a)                                                                                ##STR9## 90.8 133-4                                                                              51.8                                                                             5.0                                                                             3.2                                                                             7.3                                                                             18.1                                                                             51.4                                                                             5.1                                                                             3.3                                                                             7.4                                                                             18.0                            (3a)                                                                                ##STR10##                                                                              81.8 148-9                                                                              50.7                                                                             4.7                                                                             3.3                                                                             7.5                                                                             18.7                                                                             51.0                                                                             4.9                                                                             3.5                                                                             7.2                                                                             19.2                            (2a)                                                                                ##STR11##                                                                              78.8 162-3                                                                              49.5                                                                             4.4                                                                             3.4                                                                             7.8                                                                             19.4                                                                             49.8                                                                             4.6                                                                             3.4                                                                             7.2                                                                             19.9                            __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR12##                                                                                             Anal.                                                                         Calculated                                                                              Found                                      Example                                                                            X         Yield, %                                                                           M.P., °C.                                                                   C  H N S  C  H N S                                   __________________________________________________________________________    (5b)                                                                                ##STR13##                                                                              56.2 167-8                                                                              61.6                                                                             5.2                                                                             4.2                                                                             9.7                                                                              61.3                                                                             5.1                                                                             4.4                                                                             9.5                                 (1b) NHSO.sub.2 CH.sub.3                                                                     52.7 172-3                                                                              60.5                                                                             4.8                                                                             4.4                                                                             10.1                                                                             59.7                                                                             5.1                                                                             4.5                                                                             10.7                                (4b)                                                                                ##STR14##                                                                              51.1 137-40                                                                             66.5                                                                             4.5                                                                             3.7                                                                             8.5                                                                              64.6                                                                             4.4                                                                             3.7                                                                             8.2                                 (6b)                                                                                ##STR15##                                                                              76.7 59-60                                                                              66.5                                                                             4.5                                                                             3.7                                                                             8.5                                                                              65.8                                                                             4.3                                                                             3.7                                                                             9.0                                 (7b)                                                                                ##STR16##                                                                              84.33                                                                              112-14                                                                             63.5                                                                             5.9                                                                             3.9                                                                             8.9                                                                              63.3                                                                             5.5                                                                             3.8                                                                             8.7                                 (3b)                                                                                ##STR17##                                                                              43.9 106-7                                                                              62.6                                                                             5.5                                                                             4.1                                                                             9.3                                                                              62.8                                                                             5.7                                                                             4.2                                                                             8.7                                 (2b)                                                                                ##STR18##                                                                              70.0 124-9                                                                              57.6                                                                             4.9                                                                             3.9                                                                             8.9                                                                              57.9                                                                             5.3                                                                             4.0                                                                             9.4*                                __________________________________________________________________________     *Analysis calculated for 65% product, 35% 4'-ethanesulfonamidophenyl          4(2-bromoethyl)benzoate.                                                 

EXAMPLES 8-12 Polymerization of 4-(α-Methanesulfonamido)tolyl4-vinylbenzoate

A solution of 8.0 g of 4-(α-methanesulfonamido)tolyl 4-vinylbenzoate and72 ml of N,N-dimethylformamide was purged with nitrogen.2,2'-Azobis(2-methylpyropionitrile) (0.04 g) was added and the solutionwas heated in a 60° C. bath with nitrogen bubbling for 17.5 hours. Thesolution was poured into ether to precipitate polymer which wasisolated, rinsed again with ether and dissolved in acetone containing asmall amount of water. The solution was poured into ether to precipitatepolymer which was collected and dried. The yield of polymer was 4.7 g(58.8% conversion).

Analysis calculated for C₁₇ H₁₇ NO₄ S: C, 61.6; H, 5.2; N, 4.2; S, 9.7.Found: C, 61.1; H, 5.2; N, 4.4; S, 10.0.

The inherent viscosity was determined to be 0.43 and the glasstransition temperature was measured as 158° C.

The above procedure was followed to achieve the synthesis of thepolymers listed in Table III which follows:

                                      TABLE III                                   __________________________________________________________________________     ##STR19##                                                                                                  Anal.                                                            Conver-                                                                            I.V.    Calculated                                                                              Found                                 Example                                                                            X           sion, %                                                                            dl/g                                                                             Tg, °C.                                                                     C  H N S  C  H N S  Sol.                        __________________________________________________________________________     8   CH.sub.2 NHSO.sub.2 CH.sub.3                                                              58.8 0.43                                                                             158  61.6                                                                             5.2                                                                             4.2                                                                             9.7                                                                              61.1                                                                             5.2                                                                             4.4                                                                             10.0                                                                             acetone                      9   NHSO.sub.2 CH.sub.3                                                                       73.3 0.69                                                                             188  60.6                                                                             4.7                                                                             4.4                                                                             10.1                                                                             58.3                                                                             4.9                                                                             4.5                                                                             10.6                                                                             "                           10   NHSO.sub.2 CH.sub.2 CH.sub.3                                                              60.6 0.60                                                                             161/211                                                                            61.6                                                                             5.2                                                                             4.2                                                                             9.7                                                                              60.2                                                                             5.8                                                                             4.0                                                                             9.2                                                                              "                           11   NHSO.sub.2(CH.sub.2  ).sub.2CH.sub.3                                                      76.3 0.95                                                                             149  62.6                                                                             5.5                                                                             4.1                                                                             9.3                                                                              62.3                                                                             5.9                                                                             4.1                                                                             8.7                                                                              "                           12                                                                                  ##STR20##  58.7 1.11                                                                             156  66.5                                                                             4.5                                                                             3.7                                                                             8.5                                                                              66.0                                                                             4.7                                                                             3.4                                                                             8.7                                                                              "                           __________________________________________________________________________

EXAMPLES 13-17 Photographic Elements

Dopes were prepared according to the formula given below and were coatedat about 100 microns wet thickness on subbed poly(ethyleneterephthalate) support.

    ______________________________________                                        Phthalaldehyde          0.320   g                                             Cobalt (III) hexammine trifluoro-                                                                     0.200   g                                             acetate                                                                       2-Isopropoxy-1,4-naphthoquinone                                                                       0.0108  g                                             SF-1066 Surfactant (a stable                                                                          0.040   g                                             copolymer of dimethyl polysiloxane                                            and a polyoxyalkylene ether sold                                              by General Electric Co.)                                                      Polymeric binder        1.90    g                                             Acetone                 7.60    g                                             ______________________________________                                    

The coating block was set at 90° F. during coating and for one minutethereafter, then heated at 140° F. for five minutes for further drying.The sensitometry of the films was determined from prints prepared bycontact exposing the film for about eight seconds through a 0.3 log Estep tablet in an IBM Microcopier IID, Model 9954 exposing apparatus andthen developing the image by contacting the back of the film for fiveseconds to a hot block set at 140° C. Results are recorded in thefollowing Table IV:

                  TABLE (IV)                                                      ______________________________________                                         ##STR21##                                                                    Ex-                           Rel.   Maximum                                  am-                  Polymer  Speed  Neutral                                  ple  X               Tg (°C.)                                                                        (Log E)                                                                              Density                                  ______________________________________                                        13   CH.sub.2 NHSO.sub.2 CH.sub.3                                                                  158°                                                                            -0.20  1.6                                      14                                                                                  ##STR22##      156°                                                                            -0.90  0.5                                      15   NHSO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                         149°                                                                            -0.50  1.9                                      16   NHSO.sub.2 CH.sub.2 CH.sub.3                                                                  161°                                                                            -0.90  1.6                                      17   NHSO.sub.2 CH.sub.3                                                                           158°                                                                            -0.30  2.2                                      ______________________________________                                    

The invention has been described in detail with particular reference topreferred embodiment thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A polymer comprising:(a) about 1 to 100 molepercent of one or more units having the formula: ##STR23## wherein: Rand R' are independently selected from the group consisting of H, halideand alkyl;Ar and Ar' are independently arylene; X is selected from thegroup consisting of NHSO₂ R₂, CH₂ NHSO₂ R₂ and SO₂ NHR² and R² isselected from the group consisting of alkyl, aryl and aralkyl, and (b) 0to 99 mole percent of one or more additional polymerized ethylenicallyunsaturated polymerizable monomers.
 2. The polymer of claim 1 wherein Rand R' are hydrogen, Ar and Ar' are phenylene and X is SO₂ NHR² and R²is CH₃.
 3. The polymer of claim 1 having an inherent viscosity withinthe range of from about 0.4 to about 1.2.